DE2714897A1 - HYDRO-SOLUBLE EARTH ALKALINE SALT OF POLYMERIZES OF ACRYLIC ACID AND THEIR USE AS SIZING AGENTS - Google Patents

Description

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27U897

Water-soluble alkaline earth salts of polymers of acrylic acid and their use as sizing agents

The invention relates to water-soluble alkaline earth salts of copolymers from acrylic acid and / or methacrylic acid and acrylonitrile and / or methacrylonitrile and the use of the copolymers as a sizing agent for staple fiber yarns.

In the textile industry it is common practice to use cotton yarn or other staple fiber yarns containing cellulose fibers with hot liquors of water-soluble, natural or synthetic To treat products before they are further processed on the loom. This yarn pretreatment, which is called in technical jargon referred to as finishing, is carried out to increase the mechanical resistance of the webs so that they can Can withstand high stresses during the weaving process better than in the raw and untreated state.

For example, DT-AS 15 9 ¹ · 905 discloses the use of water-soluble sodium or ammonium salts of polymers made from acrylonitrile and acrylic acid for sizing staple fiber yarns. Although these sizing agents are generally extremely effective, the fiber coatings produced with them are sensitive to moisture, so that the yarns sized with these agents stick to one another in a humid climate and show abrasion. Both of these lead to defective fabric and machine downtime.

The invention is based on the object of a water-soluble polymer to make available based on acrylic acid or methacrylic acid, which can be used as a sizing agent and that forms moisture-insensitive films on the sized staple fiber yarns compared to the known sizing agents.

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The object is achieved according to the invention with water-soluble alkaline earth salts from polymers

(a) 90 to 30 wt.% acrylic acid and / or methacrylic acid,

(b) 10 to 70 Gew.ii acrylonitrile and / or methacrylonitrile and possibly

(c) up to 30% by weight of acrylamide and / or methacrylamide and / or an acrylic and / or methacrylic acid ester.

15 #ige solutions of these Polymerisatsalze in water at 85 ⁰ C have viscosities of 50 to 1.000 cps (measured with a Brookfield viscometer RVT at 100 revolutions per minute). The copolymers preferably contain up to 20 wt.% Of the monomers (c) in copolymerized form, wherein Acrylsauremethylester as (meth) Acrylester of particular interest is "

The alkaline earth metal salts mentioned are surprisingly in boiling Water soluble and are ideally suited as sizing agents for staple fiber yarns 0 The new sizing agents are planned All things are important for sizing staple fiber yarns which consist of cellulose fibers or contain at least 30% by weight thereof. They are mainly used for sizing pure cellulose fibers or fiber blends of cellulose and polyester fibers or Acrylonitrile polymer fibers are used. Endless viscose rayon fibers can also be sized with the alkaline earth salts.

The copolymers are polymerized by known processes of the monomers produced. A manufacturing process for the Copolymers are known, for example, from US Pat. No. 2,819,109. The monomer mixture is continuously or discontinuously with the help of radical polymerization initiators, preferably polymerized in water. If one already uses the alkaline earth metal salts of acrylic acid during the polymerization of the monomers or methacrylic acid is used, one receives directly the invention

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appropriate substances »Acrylic acid and / or is preferably polymerized Methacrylic acid with acrylonitrile and / or methacrylonitrile and optionally the corresponding amides in water in the manner of a Precipitation polymerization and then neutralizes the copolymer containing carboxyl groups with alkaline earth metal hydroxides. The resulting aqueous solutions of the alkaline earth salts of the copolymers can be used directly as sizing agents.

Particularly effective sizing agents are prepared by neutralizing up to 40% of the acrylic acid used in the polymerization with alkali or ammonium ions, polymerizing in aqueous solution and then neutralizing the resulting aqueous polymer solution with alkaline earth salts. The complete neutralization of the copolymers is preferably carried out with the oxides or hydroxides of calcium and / or magnesium. A production process for the copolymers in which partially neutralized acrylic acid or methacrylic acid is used is known from DP-AS 20 04 676. The copolymers used as sizing agents are at least 50 % neutralized.

However, one can also use the precipitation polymerization in water isolate the copolymers obtained, dry and mix with dry, powdery alkaline earth metal hydroxides. The powdery mixtures can be dissolved in water without difficulty to give a clear solution.

The copolymers of the monomers of components (a), (b) and, if appropriate, (c) can also be prepared by the reverse process Suspension polymerization, which is known from DT-PS 10 81 228 and according to the inverse emulsion polymerization process according to DT-PS 10 89 173 are produced. The substances according to the invention are, unless you already have the alkaline earth salts the acrylic acid or methacrylic acid used in the polymerization, by neutralizing the copolymers with Alkaline earth hydroxides obtained.

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The materials of the invention preferably contain as component (a) to yj Gu Uevi. '/ Ό acrylic acid as component (b) 13-65 Gew.Ü acrylonitrile. They may optionally contain up to 20 wt.% Of acrylamide and / or methacrylamide. The viscosity of the alkaline earth polymer salts according to the invention in 15% aqueous solution at a temperature of 85 ° C. is from 50 to 1,000, preferably from 200 to 600, cP. The viscosities were each measured with a Brookfield Viscometer RVT at 100 revolutions per minute.

The substances according to the invention are mainly used as sizing agents, but can also be used as paper thickeners, printing thickeners, Textile finishing agents and adhesives are used in the construction sector. The new products are of particular importance Acquired as a sizing agent for staple fiber yarns, the cellulose fibers contain or consist of. The staple fiber yarns are usually in one with aqueous solutions of the sizing agent Treated temperature range from 70 to 95 ° C. Depending on the composition of the copolymer, one liter Dissolve water up to 500 g of the copolymer salt. For the use of the alkaline earth salts of the copolymers as sizing agents 1 to 20% strength by weight aqueous solutions are generally used.

The sizing effect achieved with the products according to the invention can be further improved by using mixtures of alkaline earth and alkali salts of copolymers the end

(a) 90 to 30% by weight of acrylic acid and / or methacrylic acid,

(b) 10 to 70% by weight of acrylonitrile and / or methacrylonitrile

and if necessary

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(c) up to 30% by weight of acrylamide and / or methacrylamide and / or an alkyl ester of acrylic and / or methacrylic acid with mostly 1 to ^ carbon atoms in the alcohol residue

begins.

The viscosity of the copolymer salt mixtures in a 15% strength by weight solution at a temperature of 85 ° C. is likewise 50 to 1,000 cP. The alkali salts of the copolymers mentioned are above all the ammonium salts or sodium salts. However, it is also possible to use ammonium salts derived from primary, secondary, tertiary and quaternary amines. In the mixtures, at least 60 % of the carboxyl groups should be present as alkaline earth salts, preferably as calcium and / or magnesium salts. The pH of the sizing agents is generally from 5 to 12 and is preferably in the range from 6.0 to 7.5. The use of mixtures of alkaline earth and alkali salts of copolymers of acrylic acid and acrylonitrile results in improved sizing effects, which can be demonstrated in a noticeable increase in the abrasion index and a considerable reduction in the number of warp thread breaks per loom hour. As with the use of the pure alkaline earth metal salts of the copolymers, mixtures of the alkaline earth metal and alkali metal salts of the copolymers also give moisture-insensitive films with high water absorption of the size film. The good thermal stability of the substances according to the invention in comparison with the known ammonium salts of the copolymers is also noteworthy.

The invention is illustrated in more detail by means of the following examples. The parts given in the examples are parts by weight, the percentages relate to the weight of the substances. The viscosity the copolymers were in 15 # aqueous solution at a temperature of 85 ° C in a Brookfield viscometer RVT at 100 revolutions per minute measured.

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The abrasion index, a criterion for the sizing effect in staple fibers, was determined according to the instructions of E, Kenk, Textil-Praxis 7, 690 (1952) on a commercially available yarn abrasion tester.

The pendulum hardness as a criterion for the moisture sensitivity of the sizing film was determined on an Albert-König pendulum hardness tester at 65 % relative humidity / 20 ° C (P ₁ ) and 85 % relative humidity / 20 ° C (P ₂ ).

The products according to the invention are according to the method described in O.Z. 31 5Ö5 granted Recover gauge and can be reused in finishing.

For the following examples and comparative examples, the following were used Sizing agents used:

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Size 1 Mg salt of a copolymer of 50 wt. Acrylic acid and 50 wt.% Of acrylonitrile, viscosity 120 cP

Size 2 Mg salt like size 1, but with a viscosity of 700 cP

Size 3 Ca salts of a copolymer of 50 % acrylic acid and 50 % acrylonitrile, viscosity 120 cP

Size 4 ' NHju salt of a copolymer of 75 % acrylic acid and 25 % acrylonitrile, viscosity 290 cP

Sizing 5 Mg salt like Sizing 1, but with a viscosity of 305 cP

ο Sizing 6 Ca salt like Sizing 3, but with a viscosity of 275 cP

oo Size 7 Na salt from the copolymer of size 1

Size NH ^ salt from the copolymer of size 1 (J ₁ size 9 polyvinyl alcohol with a degree of polymerisation of approx. 1,400, ^ degree of hydrolysis 86 to 89 %

¹ ^ Sizing 4 was produced on the basis of Example 1 of DT-AS 20 04.

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example 1

On a laboratory sizing machine, which consists substantially of a pair of nip rollers with a heated size box, a flow-through with hot air of 170 ⁰ C drying channel a length of 190 cm and a diameter of 7 cm and an operating with constant tension winder was a carded ßaumwoll staple fiber yarn Nm bö / l treated with a 10%, 80 ⁰ C hot aqueous solution of size 1. Four individual yarns were combined to form a strand before immersion in the sizing liquor, and after a single immersion, they were squeezed out so that a size application of 12.7% by weight, based on the dry weight of the yarn, was obtained. After passing through the drying tunnel at a speed of 10 m / min, the strand of yarn was divided into the four original individual yarns on four vertical rods and wound up with constant tension. After the sized material had been air-conditioned for 24 hours at 65% relative humidity and a temperature of 20 ° C., the abrasion index was measured. The sizing film is insensitive to moisture and not sticky.

For comparison, the same yarn was used with 10 # aqueous solutions treated under the same conditions with the known sizes 7, 8 and 9 «, Table 1 shows the sizing results «,

Production of the size 1

A solution of 1.35 kg of potassium peroxide sulfate in 523 liters of fully demineralized water is placed in a stirred autoclave. The gas space is pressed in 3 times with 5 bar nitrogen each time and depressurized. The mixture is then heated up with vigorous stirring and a homogeneous mixture evenly on 135 kg of acrylonitrile and 135 kg of acrylic acid were metered in at 70 ° C inner temperature within h hours. Synchronously with this feed, a solution of 700 g of sodium disulfite (Na ₂ SpOc-) in 35 l of deionized water is metered in evenly.

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The third feed is one hour after the start of the first feed a solution of 1.8 kg of potassium peroxydisulfate in 90 liters full Demineralized water is metered in evenly over a period of 3 hours.

The total polymerization time is 4 hours at 7OC and

1 hour at 80 ° C.

Then unpolymerized acrylonitrile is released through outgassing largely removed with stirring at -0.5 bar vacuum and 80 ° C. The fine polymer precipitate is then added by uniformly adding 100 liters of a 10% aqueous ammonium sulfate solution deliberately coarsened for 15 minutes.

Now the suspension is cooled with stirring and after interposition spray-dried on a 2 mm sieve.

The diameter of the spray dried product is almost complete less than 0.2 mm. The product can be mixed homogeneously well with the necessary quantities of powdered magnesium oxide.

As a polyacid, it has an acid number of approx. 300 and a K value of 70 (1 / iig in dimethyl sulfoxide; according to Fikentscher).

Manufacture of the sizing solution:

The powdery polyacid, as such or in the form of its aqueous suspension, is mixed with the stoichiometric amount of magnesium oxide (2 COOH: 1 MgO; 100 g polymer + 14 g MgO) and at about 90 ^° C. to give a 15 wt. % solution dissolved in water. The viscosity of the solution is approx. 120 cP at 85 ° C.

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Table 1 example

Sizing order wt

Abrasion rating

Pendulum hardness

1) Plain 1

976

116

27

Comparative examples

la) Plain 7

b) Simple 8

c) Conciliation 9

13.2 1.005 10 5 13.2 980 22nd 14th 12.7 730 20th 7th

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Example 2

A polyester-cotton yarn was used on the apparatus given in Example 1 (65: 35 »Nm 69/1) each sized with 15 Stigen aqueous solutions of the sizing agents given in Table 2. The temperature of the size liquor was 80 ° C. in each case. The results are summarized in Table 2:

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Table 2

Examples Sizing order
Qew.? Abrasion rating Pendulum hardness
P ₁ P ₂ 27 2a) Placement 1 16.6 2,472 116 30th b) Conciliation 2 16.3 2,617 125 to Comparative examples <0 5 QO
• Τ 2a) Finishing 7 16.6 2,400 10 14th Ο b) Simple 8 16.3 2,327 22nd 7th 053 c) Conciliation 9 16.4 2,568 20th

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Example 3

A polyester-cotton yarn (65:35, Nm 69/1) was each with 15 Jiigen aqueous solutions at a temperature of 80 ° C. with the sizing agents given in Table 3. In the Table 3 summarizes the results. You can clearly see the synergistic effect on mixtures of alkali and Alkaline earth salts of acrylic acid copolymers based.

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Tabel

Examples of sizing agents

Sizing order weight?

3a) b)

c)

d)

Size 4 + size in a weight ratio of 1: 1

Size 4 + size in a weight ratio of 1: 1

Plain plain

16.4 16.3

16.8 16.7

Comparative example

3a) Sizing

16.5

Abrasion rating

2,938 2,383

2,405 '1,196

1,175

The films obtained in Examples 3a to d are insensitive to moisture and non-sticky, while in Comparative Example 3a, moisture-sensitive Films result.

In Examples 3a and 3b, 38 * 1 % of the carboxyl groups in the copolymer mixture are neutralized by alkaline earth metal.

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Example 4

Sucker on a sizing machine with cylinders 7 2,000 m Cotton Nm 6o / l were approximately sized under conventional conditions at 90 ⁰ C liquor temperature according to the following recipe. The liquor uptake was approx. 100 Ji, the temperature of the drying cylinders 120-140 ° C. The size liquor was prepared in a turbo cooker (15 min, 105 ° C.).

Prescription ; 24 kg size 1

0.1 kg of stearic acid monoglyceride 300 l of water

The sized warp weighed 9.8% by weight of size 1, based on the dry weight of the yarn, and had a residual moisture content of 8% by weight . It was woven on an automatic weaving machine with a weft insertion rate of 220 / min at 70 % relative humidity and a temperature of 20-22 ° C. to form an article, the technical weaving data of which are recorded in Table 4.

Table 4 Fabric data of the cotton article

Warp density: 41 threads / cm

Weft density: 42 threads / cm

Weft yarn: Nm bO / 1

Total thread count: 6050

Type of weave: canvas 1/1

A statistical evaluation of the weaving test resulted in a number of 0.22 warp thread breaks per loom hour.

Comparative tests carried out under the same conditions with 24 kg of size 8 and size 7 led to articles in which warp thread breaks of 0.45 or 0.56 per loom hour were measured. «All fabrics were first-class quality.

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Example 5

Under the conditions specified in Example 4, each approx. 2,000 m of cotton yarn Hm 68/1 were sized according to the following recipes

Recipe 1 Recipe 2

38 kg size 4 30 kg size 4

460 1 water 8 kg size 1

460 1 water

Recipe 3 Recipe 4

30 kg size 4 38 kg size 1

8 kg size 3. 460 1 water 460 1 water

For recipes 2 and 3, 13.7 % of the carboxyl groups in the copolymers were neutralized by alkaline earths.

The sized warps were woven on Sulzer automatic weaving machines with a weft insertion rate of 240 / min at 76-78 % relative humidity and a temperature of 20-22 ° C. to form the article characterized in Table 5.

Tabel 5 Fabric data of the cotton article

Warp density: 43 threads / cm

Weft density: 43 threads / cm

Weft yarn: Nm 68/1

Total warp thread count: 6,372

Type of weave: canvas 1/1

The determination of the abrasion index and the statistical evaluation of the warp thread breaks during the weaving process gave the following results (Table 6):

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Table 6 Recipe for finishing application abrasion number of warp thread breaks

per loom hour

1 (comparison) 8.2 wt.

2 8.4 wt. 2

3 9.0 wt

4 8.5 wt. *

^<£> The warp thread breaks per loom hour are essential in the comparison test

* - higher than with the formulations according to the invention, ο

1,163 1.07 1,486 0.74 1,257 0.76 1,145 0.85

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On the sizing machine mentioned in Example 7, approx. 2,000 m of polyester-cotton yarn (65: 35J Nm 50/1) were produced according to the following Formulations settled. The liquors were made by boiling for 10 minutes in a sucker pressure cooker at one temperature of 105 ° C. The temperature of the liquor in the sizing trough was 90 ° C.

Recipe 1 (comparative example) Recipe 2

30 kg size 4 24 kg size 4

300 1 water 6 kg size 5

300 l of water

Recipe 3

24 kg size 4
6 kg size 6
300 l of water

The recipes 2 and 2 are examples according to the invention, \ J>, J>% of the carboxyl groups of the copolymers are each neutralized by alkaline earths.

All warps were rewaxed with 0.15 to 0.20 wt. JS - based on the dry warp yarn - of a commercially available melt wax and on high-performance automatic weaving machines with a weft insertion of 220 / min at 70 % relative humidity / 20-22 ° C. to that in the table 7 specified poplin items are woven.

Table 7 45.5 Warp density: 25.0 Weft density: Nm 50/1 Weft: 7.180 Total thread count: Canvas 1/1 Type of binding:

The determination of the abrasion rating as well as the statistical evaluation the warp thread breaks during the weaving process resulted in the following values (Table 8):

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Table 8

Sizing recipe recipe abrasion rate warp thread breaks per

Loom lesson

1 (comparative) 14.4 wt.% 2,421 0.40

2 14.8 wt.% 4 "0.17 96l

3 14.7 wt. 4,795 0.19

⁰⁰ All fabrics were 1st choice quality, but the number of warp thread breaks is X--

o per loom hour significantly higher in the example according to the prior art _o (recipe 1) than in the examples according to the invention. cn

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CX) CO

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Example 7

About 2,000 m of the poplin fabric specified in Example 6 and brushed to remove the suction dust, which had been prepared from the sizing process with an application of 9.1% by weight of size 1, was pulled through a dipping trough at a speed of 40 m / min , which was charged with fully demineralized water that had a temperature of 50 ⁰ C. The trough was immersed twice for 1 s each time. After each immersion, water adhering to the surface was wiped away. After a swelling time of 10 s in the air passage, the material was squeezed out at maximum pressure using a padder squeegee. A 7 # size liquor with a yield of 47 % of theory of recoverable active substance was obtained. Carded cotton yarn Nm 20/1 was sized on the laboratory sizing machine described in Example 1 at a liquor temperature of 80 ° C. in such a way that a size application of 5 to 5.5 Weight? of size - based on the dry weight of the warp yarn. The determination of the abrasion index on both yarns conditioned for 24 hours in a standard climate resulted in practically equivalent sizing effects (Table 9).

Table 9

Sizing agent Sizing layer abrasion rating

Original size 1 5.5 weight # 1.598

Regenerated size 1 5.3% wt. 1,621

This example shows that the sizing agent according to the invention can be recovered and reused as a sizing agent

BASF Aktiengesellschaft

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Claims (5)

Claims l.j Water-soluble alkaline earth salts made from copolymers (a) 90 to 30 Qe-w.% acrylic acid and / or methacrylic acid, (b) 10 to 70 wt. Acrylonitrile and / or methacrylonitrile and if necessary (c) up to 30 wt. Acrylamide and / or methacrylamide, in 15? aqueous solution have a viscosity from 50 to 1,000 cps at a temperature of 85 ⁰ C. 2. Use of the water-soluble alkaline earth salts according to claim 1 as sizing agents for staple fiber yarns. 3. Use according to claim 2, for staple fiber yarns consisting of cellulose fibers or at least 30 wt. of that contain. 4. Use of mixtures of alkaline earth and alkali salts from copolymers (a) 90 to 30 wt. Acrylic acid and / or methacrylic acid, (b) 10 to 70 wt. Acrylonitrile and / or methacrylonitrile and optionally (c) up to 30 wt. Acrylamide and / or methacrylamide and / or an acrylic and / or methacrylic acid ester, in 15? aqueous solution at a temperature of 85 ⁰ C have a viscosity from 50 to 1,000 cP, as a sizing agent for staple fiber yarns. ^99/77 809840/0537 " ² " ORlG (NAL INSPECTED - 2 - U.Z. 32 521 27U897 5. Use according to claim H, characterized in that _t
ammonium or sodium salts are used as alkali salts and magnesium or calcium salts are used as alkaline earth salts. 809840/0537